CN119365518A

CN119365518A - Resin composition, cured product, sealing material, adhesive, insulating material, coating, prepreg, multilayer body and fiber-reinforced composite material

Info

Publication number: CN119365518A
Application number: CN202380042204.9A
Authority: CN
Inventors: 池田黄介; 安田祥宏; 片桐诚之
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2022-05-27
Filing date: 2023-03-06
Publication date: 2025-01-24
Also published as: US20230383047A1; JP2023174433A; TWI841278B; WO2023228509A1; JP7197047B1; TW202346465A; EP4282902A1; EP4282902B1

Abstract

提供维持优异的耐热性且潜在性优异的树脂组合物，以及固化物、密封材料、粘接剂、绝缘材料、涂料、预浸料、多层体和纤维增强复合材料。一种树脂组合物，其包含氰酸酯化合物(A)、胺加合物化合物(B)和硼酸酯(C)。Provided are a resin composition having excellent heat resistance and excellent potential, and a cured product, a sealing material, an adhesive, an insulating material, a coating, a prepreg, a multilayer body, and a fiber-reinforced composite material. A resin composition comprising a cyanate compound (A), an amine adduct compound (B), and a borate ester (C).

Description

Resin composition, cured product, sealing material, adhesive, insulating material, coating material, prepreg, multilayer body, and fiber-reinforced composite material

Technical Field

The present invention relates to a resin composition, a cured product, a sealing material, an adhesive, an insulating material, a coating material, a prepreg, a multilayer body, and a fiber-reinforced composite material. In particular, it relates to a resin composition or the like containing a cyanate ester compound.

Background

Heretofore, cyanate ester compounds have been known as thermosetting resins that form triazine rings upon curing. The cured product obtained from the cyanate ester has excellent properties such as high glass transition temperature, low dielectric constant and dielectric loss tangent, excellent electrical insulation, and excellent flame retardancy. Accordingly, cyanate ester compounds are widely used as raw materials for electric and electronic materials, structural composite materials, adhesives, and other various functional polymer materials (patent document 1, etc.).

Prior art literature

Patent literature

Patent document 1 Japanese patent application laid-open No. 2021-195390

Disclosure of Invention

Problems to be solved by the invention

As described above, a resin composition containing a cyanate ester compound was studied. And in recent years, the demand thereof is expanding further. For example, the use in aerospace material applications and the like can also be expected.

On the other hand, from the viewpoint of handleability and physical distribution rationalization, it is desired that the resin composition containing the cyanate ester compound can be stored at normal temperature, and from the viewpoint of improving productivity, curability, particularly, curing at a temperature of a predetermined temperature or less is desired. In particular, for resin compositions for prepregs, the potential (for example, stability of a resin composition at about 80 ℃ or less and curability of a resin composition at about 100 to 185 ℃) is demanded. In addition, a resin composition containing a cyanate ester compound is also required not to adversely affect the heat resistance inherent therein.

The present invention has been made to solve the above problems, and an object thereof is to provide a resin composition which maintains excellent heat resistance and is excellent in potential, and a cured product, a sealing material, an adhesive, an insulating material, a coating material, a prepreg, a multilayer body, and a fiber-reinforced composite material.

Solution for solving the problem

Based on the above-described problems, the present inventors have studied and found that the above-described problems can be solved by blending an amine adduct compound and a boric acid ester with a cyanate ester compound.

Specifically, the above problems are solved by the following means.

<1> A resin composition comprising a cyanate ester compound (A), an amine adduct compound (B) and a boric acid ester (C).

<2> The resin composition according to <1>, wherein the aforementioned cyanate ester compound (a) contains at least 1 selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II).

(In the formula (I), ar ₁ each independently represents an aromatic ring, ra each independently represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, the alkyl group or the aryl group in Ra optionally having a substituent, a represents the number of bonding to a cyanooxy group bonded to Ar ₁, each independently is an integer of 1 to 3, b represents the number of bonding to Ra bonded to Ar ₁, each independently represents a number obtained by subtracting (a+2) from the number of substitutable groups of Ar ₁, c is an integer of 1 to 50, and X each independently represents any one of a single bond, a divalent organic group having 1 to 50 carbon atoms, a sulfonyl group (-SO ₂ -), a divalent sulfur atom (-S-) or a divalent oxygen atom (-O-)

(In the formula (II), ar ₂ represents an aromatic ring, rb independently represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, wherein the alkyl group or the aryl group in Rb may have a substituent; d represents the number of cyano groups bonded to Ar ₂, which is an integer of 2 to 3; e represents the number of Rb bonded to Ar ₂, which is a number obtained by subtracting (d+2) from the number of substitutable groups of Ar ₂.)

<3> The resin composition according to <2>, wherein X in the above formula (I) each independently represents a divalent linking group selected from the group consisting of the following formulas (III) to (XIV).

(In the formula (III), ar ₃ each independently represents an aromatic ring, rc, rd, rg and Rh each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, the alkyl group or the aryl group in Rc, rd, rg and Rh optionally having a substituent, re and Rf each independently represent any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, the alkyl group or the aryl group in Re and Rf optionally having a substituent, and f represents an integer of 0 to 5.)

(In the formula (IV), ar ₄ each independently represents an aromatic ring, ri and Rj each independently represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, the alkyl group or the aryl group in Ri and Rj optionally having a substituent, and g represents an integer of 0 to 5.)

(In the formula (VIII), h represents an integer of 4 to 7, and in the formula (XIII), rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

<4> The resin composition according to any one of <1> to <3>, wherein the cyanate ester compound (A) contains at least 1 or more selected from the group consisting of a compound represented by the following formula (XV) and a compound represented by the following formula (XVI).

(In the formula (XV), ar ₅ each independently represents an aromatic ring; rl each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxymethylene group, and a group obtained by connecting 2 or more of these, rm and Rn each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, the alkyl group or the aryl group in Rm and Rn optionally having a substituent; i represents the number of cyano groups bonded to Ar ₅ and is an integer of 1 to 3; j represents the number of bonding Rm bonded to Ar ₅, represents the number obtained by subtracting (i+2) from the number of substitutable groups of Ar ₅; k represents the number of bonding Rn bonded to Ar ₅, represents the number obtained by subtracting 2 from the substitutable group of Ar ₅; l represents an integer of 1 or more; m represents an integer of 1 or more, and each of the repeating units is an arbitrary arrangement.)

( In the formula (XVI), ar ₆ each independently represents an aromatic ring, ro each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxymethylene group, or a group obtained by connecting them, rp and Rq each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, the alkyl group or the aryl group in Rp and Rq optionally having a substituent, n represents an integer of 2 to 3 as the number of cyano groups bonded to Ar ₆, o represents the number of bonds of Rp bonded to Ar ₆, represents the number obtained by subtracting (n+2) from the number of substitutable groups of Ar ₆, and p represents the number of bonds of Rq bonded to Ar ₆, and represents the number obtained by subtracting 2 from the number of substitutable groups of Ar ₆. q represents an integer of 1 or more. )

The resin composition according to any one of <1> to <4>, wherein the content of the amine adduct compound (B) is 0.01 to 30 parts by mass based on 100 parts by mass of the cyanate compound (A).

The resin composition according to any one of <1> to <5>, wherein the content of the boric acid ester (C) is 0.01 to 15 parts by mass based on 100 parts by mass of the cyanate ester compound (A).

<7> The resin composition according to any one of <1> to <6>, further comprising a phenol compound (D).

<8> The resin composition according to <7>, wherein the content of the phenol compound (D) is 1 to 20 parts by mass based on 100 parts by mass of the cyanate ester compound (A).

<9> The resin composition according to any one of <1> to <8>, further comprising a toughness imparting agent (E).

<10> The resin composition according to <9>, wherein the toughness imparting agent (E) comprises a thermoplastic resin.

<11> The resin composition according to <9> or <10>, wherein the toughness imparting agent (E) comprises a powdery resin.

The resin composition according to any one of <9> to <11>, wherein the content of the toughness imparting agent (E) is1 to 40 parts by mass based on 100 parts by mass of the cyanate ester compound (A).

<13> The resin composition according to any one of <1> to <11>, wherein the content of said amine adduct compound (B) is 0.01 to 30 parts by mass based on 100 parts by mass of said cyanate compound (A),

The content of the boric acid ester (C) is 0.01-15 parts by mass relative to 100 parts by mass of the cyanate ester compound (A),

The resin composition further comprises a phenol compound (D),

The content of the phenol compound (D) is 1 to 20 parts by mass based on 100 parts by mass of the cyanate compound (A).

<14> The resin composition according to <13>, further comprising a toughness-imparting agent (E), wherein the content of the toughness-imparting agent (E) is 1to 40 parts by mass based on 100 parts by mass of the cyanate ester compound (A).

<15> A cured product of the resin composition according to any one of <1> to <14 >.

<16> A sealing material comprising the resin composition according to any one of <1> to <14 >.

<17> An adhesive comprising the resin composition according to any one of <1> to <14 >.

<18> An insulating material comprising the resin composition according to any one of <1> to <14 >.

<19> A coating material comprising the resin composition according to any one of <1> to <14 >.

<20> A prepreg comprising a substrate and the resin composition according to any one of <1> to <14 >.

<21> A multilayer body formed of the prepreg according to <20 >.

<22> A fiber-reinforced composite material comprising reinforcing fibers and a cured product of the resin composition according to any one of <1> to <14 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition, which maintains excellent heat resistance and is excellent in potential, and a cured product, a sealing material, an adhesive, an insulating material, a paint, a prepreg, a multilayer body, and a fiber-reinforced composite material can be provided.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment described below is an example for explaining the present invention, and the present invention is not limited to the present embodiment.

In the present specification, "to" is used in a meaning including numerical values described before and after the numerical values as a lower limit value and an upper limit value.

In the present specification, the values of the physical properties and the characteristic values are set to values at 23 ℃ unless otherwise specified.

The measurement method and the like described in the standard shown in the present specification are different depending on the year, and are based on the 2022, 1 and 1 day standard unless otherwise specified.

In the present specification, the resin solid component means components other than the filler and the solvent, and includes the cyanate ester compound (a), the amine adduct compound (B), the boric acid ester (C), and other thermosetting compounds and other resin additive components (phenol compound (D), toughness imparting agent (E), etc.) compounded as necessary.

The resin composition of the present embodiment is characterized by comprising a cyanate ester compound (a), an amine adduct compound (B), and a borate ester (C). With such a constitution, a resin composition having excellent potential and maintaining excellent heat resistance can be obtained.

The mechanism is presumed as follows. That is, it is presumed that the nitrogen atom moiety of the amine adduct compound (B) in the resin composition of the present embodiment acts as a catalyst in curing the cyanate compound (A). On the other hand, it is presumed that boron contained in the boric acid ester (C) shields nitrogen atoms contained in the amine adduct compound (B) when the resin composition is stored, and the curing of the resin composition is suppressed, thereby ensuring the stability of the resin composition. That is, it is presumed that the amine adduct compound (B) acts as a catalyst in curing the cyanate ester compound (A) during storage. It is also presumed that the bond between the boron of the borate (C) and the nitrogen atom of the amine adduct compound (B) is broken by heating. That is, the amine adduct compound (B) functions as a catalyst for promoting the curing of the cyanate compound (a) by heating. Further, it is assumed that the boric acid ester (C) as a Lewis acid also functions as a catalyst in curing the cyanate ester compound (A). Further, it has been found that the heat resistance of the resin composition of the present embodiment can be maintained at a high level even when the amine adduct compound (B) and the boric acid ester (C) are compounded, and the present invention has been completed.

< Cyanate Compound (A) >

The resin composition of the present embodiment contains a cyanate ester compound (a).

The cyanate ester compound (a) is preferably a compound having 2 or more-OCN groups per molecule, more preferably a compound having 2 to 10-OCN groups per molecule. The cyanate (a) of the present embodiment may be a prepolymer of a cyanate compound.

More specifically, as the cyanate ester compound (a), the cyanate ester resins described in paragraphs 0027 to 0028 of jp 2022-046517 a, paragraphs 0024 to 0043 of jp 2022-046517 a, and paragraphs 0012 to 0014 of jp 2020-011065 can be referred to, and these are incorporated herein by reference.

In the present embodiment, the cyanate ester compound (a) preferably contains at least 1 selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II).

In the formula (I), ar ₁ each independently represents an aromatic ring, and examples of the aromatic ring represented by Ar ₁ include, but are not particularly limited to, phenyl, naphthyl, and the like.

In the formula (I), ra independently represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. The alkyl or aryl group in Ra optionally has a substituent.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The alkyl group may be any of linear, branched, and cyclic.

The alkenyl group having 2 to 6 carbon atoms is not particularly limited, and examples thereof include vinyl, allyl, butenyl, pentenyl, and hexenyl. Among them, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 5 carbon atoms is more preferable. The alkenyl group may be any of a linear, branched, and cyclic one.

The alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, and butoxy groups. The alkoxy group may be any of linear, branched, and cyclic.

The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include phenyl and naphthyl.

The substituent optionally provided by the alkyl group or the aryl group in Ra is not particularly limited, and examples thereof include a halogen atom, an alkyl group, a cyano group, an alkoxy group, a carbonyl group, an amino group, an imino group, a thiol group, a sulfo group, a nitro group, an acyl group, an aldehyde group, and an aryl group.

In the formula (I), a represents the number of cyano groups bonded to Ar ₁, and each independently represents an integer of 1 to 3, preferably an integer of 1 to 2, and more preferably 1.

In the formula (I), b represents the number of Ra bonds to Ar ₁, and each independently represents a number obtained by subtracting (a+2) from the number of groups that can be substituted in Ar ₁.

In the formula (I), c is an integer of 1 to 50, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and still more preferably 1.

In the formula (I), X independently represents any one of a single bond, a divalent organic group having 1 to 50 carbon atoms, a sulfonyl group (-SO ₂ -), a divalent sulfur atom (-S-) or a divalent oxygen atom (-O-). The divalent organic group having 1 to 50 carbon atoms represented by X is not particularly limited, and examples thereof include divalent organic groups (—n—r—n- (where R represents an organic group)), carbonyl groups (—co-), carboxyl groups (—c (=o) O-), carbonyl dioxide groups (—oc (=o) O-), and divalent linking groups represented by the following structures represented by the formulas (III) to (XIV), and more preferably, divalent linking groups represented by the formulas (III) to (XIV), each of which is selected from the group consisting of nitrogen numbers 1 to 10.

In the formula (III) and the formula (IV), the aromatic ring represented by Ar ₃ and Ar ₄ may be the same as the aromatic ring represented by Ar ₁, and the preferable range is the same. In the above formula, the same groups as those exemplified in Ra are exemplified as the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkoxy group having 1 to 4 carbon atoms and the substituent represented by Rc, rd, rg, rh, re, rf, ri and Rj, and the preferable ranges are also the same.

In the formula (II), ar ₂ represents an aromatic ring, and the same meaning as Ar ₁ in the formula (I) and the preferable range are the same.

In the formula (II), rb each independently represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or the aryl group in Rb may have a substituent, and the meaning and preferable range of Ra in the formula (I) are the same.

In the formula (II), d represents the number of cyanooxy groups bonded to Ar ₂ and is an integer of 2 to 3, e represents the number of Rb bonds bonded to Ar ₂, and represents the number obtained by subtracting (d+2) from the number of substitutable groups of Ar ₂.

Further, the cyanate ester compound (a) more preferably contains at least 1 or more selected from the group consisting of a compound represented by the following formula (XV) and a compound represented by the following formula (XVI).

In the formula (XV), as the aromatic ring represented by Ar ₅, the same aromatic ring as that exemplified in Ar ₁ can be exemplified, and the preferable range is also the same.

In the formula (XV), the same groups as those exemplified in Ra are exemplified as the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkoxy group having 1 to 4 carbon atoms and the substituent thereof shown in Rm and Rn, and the preferable ranges are also the same.

In the formula (XV), l represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 5.

In the formula (XV), m represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 5.

In the formula (XVI), as the aromatic ring represented by Ar ₆, the same aromatic ring as that exemplified in Ar ₁ can be exemplified, and the preferable range is also the same.

In the formula (XVI), the same groups as those exemplified in Ra are exemplified as the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, the alkoxy group having 1 to 4 carbon atoms and the substituent thereof shown in Rp and Rq, and preferable ranges are also the same.

In the formula (XVI), q represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 5.

As described above, the cyanate ester compound (a) used in the present embodiment may be a prepolymer. Examples of the prepolymer include prepolymers (containing a part of cyanate groups) which are reactants of 2 or more molecules (preferably 2 to 10 molecules) of the compound represented by the formula (I) and/or the compound represented by the formula (II). By using such a prepolymer, a resin composition excellent in handleability when a prepreg is produced can be easily produced.

The content of the cyanate ester compound (a) in the resin composition of the present embodiment is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 65 parts by mass or more, still more preferably 70 parts by mass or more, still more preferably 75 parts by mass or more, relative to 100 parts by mass of the resin solid content contained in the resin composition. When the lower limit value is not less than the above-mentioned lower limit value, the heat resistance tends to be further improved. The upper limit of the content of the cyanate ester compound (a) is an amount in which all of the resin solid components of the amine adduct compound (B) and the boric acid ester (C) are the cyanate ester compound (a), and specifically, 99 parts by mass or less, and more preferably 97 parts by mass or less, relative to 100 parts by mass of the resin solid components contained in the resin composition.

The resin composition of the present embodiment may contain only 1 kind of cyanate ester compound (a), or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

< Amine adduct Compound (B) >)

The resin composition of the present embodiment contains an amine adduct compound (B). By containing the amine adduct compound (B), a resin composition having excellent stability in storage and excellent curability in heating can be obtained.

The amine adduct compound (B) is usually solid at ordinary temperature (for example, 25 ℃) and starts to soften by heating, and the reactivity is improved. The softening temperature of the amine adduct compound (B) is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and further preferably 150 ℃ or lower, more preferably 145 ℃ or lower. When the lower limit value is not less than the above-mentioned lower limit value, the stability during storage tends to be further improved. Further, setting the upper limit value or less tends to further improve the curability. The softening temperature was determined by a test method according to JIS K7234:1986.

The amine adduct compound (B) is an adduct of an amine compound, preferably an adduct of an amine compound (preferably an imidazole compound or a compound having a tertiary amino group) and at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound and an epoxy resin, more preferably an adduct of an amine compound and at least 1 compound selected from the group consisting of a urea compound, an isocyanate compound and an epoxy resin, further preferably an adduct of an amine compound and an isocyanate compound and/or an epoxy resin.

The amine may be, for example, one having 1 or more active hydrogens in 1 molecule and 1 or more (preferably 1 to 3, more preferably 1 or 2, still more preferably 1) or more at least 1 selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups in 1 molecule, and preferably 1 or more secondary amino groups or tertiary amino groups in a molecule. As described above, the amine compound is preferably an imidazole compound or a compound having a tertiary amino group.

Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2, 4-dimethylimidazoline, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, and 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline.

Examples of the compound having a tertiary amino group include dimethylaminopropylamine, diethylaminopropylamine, di-N-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, 1, 4-bis (3-aminopropyl) piperazine, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, dimethylaminomethylphenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. Beta. -hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 1, 4-diazabicyclo [2.2.2] octane, N, N-dimethyl-N ' -phenylurea, N-dimethyl-N ' - (3, 4-dichlorophenyl) urea, tolylbis (dimethylurea), 4' -methylenebis (phenyldimethylurea), 2-mercaptopyridine, N, N-dimethylaminobenzoic acid, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N-dimethylglycine hydrazide, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide.

The urea compound is not particularly limited as long as it has at least 1 selected from the group consisting of urea bond, ureylene bond and nh—co—n. Examples thereof include urea, urea phosphate, urea oxalate, urea acetate, diacetyl urea, dibenzoyl urea and trimethyl urea.

The isocyanate compound is not particularly limited. Examples thereof include monofunctional isocyanate compounds such as n-butyl isocyanate, phenyl isocyanate and hexamethylene diisocyanate, and polyfunctional compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and 1,3, 6-hexamethylene triisocyanate.

The epoxy resin is not particularly limited. Examples thereof include polyphenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric alcohols such as glycerin and polyethylene glycol, polyglycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β -hydroxynaphthoic acid, polyglycidyl esters obtained by reacting epichlorohydrin with polybasic carboxylic acids such as phthalic acid and terephthalic acid, and glycidylamine-type epoxy resins obtained from 4, 4-diaminodiphenylmethane and m-aminophenol.

The amine adduct compound (B) used in the present embodiment may be one described in paragraphs 0067 to 0077 of Japanese patent application laid-open No. 2021-075698, paragraph 0040 to 0052 of Japanese patent application laid-open No. 2019-123825, paragraph 0030 to 0038 of Japanese patent application laid-open No. 2016-153513, paragraph 0023 of Japanese patent application laid-open No. 2013-151700, paragraph 0037 to 0051 of Japanese patent application laid-open No. 2020-200389, and paragraph 0026 to 0036 of Japanese patent application laid-open No. 2020-100684, and these contents are incorporated herein by reference.

The content of the amine adduct compound (B) in the resin composition of the present embodiment is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.5 part by mass or more, still more preferably 0.8 part by mass or more, relative to 100 parts by mass of the cyanate ester compound (a). When the lower limit value is not less than the above-mentioned lower limit value, the curing acceleration effect tends to be further improved. The upper limit of the content of the amine adduct compound (B) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass of the cyanate ester compound (a). When the upper limit value is not more than the above-mentioned upper limit value, the stability of the resin composition during storage tends to be further improved.

The resin composition of the present embodiment may contain only 1 kind of the amine adduct compound (B), or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

< Boric acid ester (C) >)

The resin composition of the present embodiment contains a boric acid ester (C). By including the boric acid ester (C), a resin composition having excellent stability in storage and excellent curability in heating can be obtained.

In this embodiment, the borate (C) is preferably a compound capable of inhibiting the activity of the nitrogen atom contained in the amine adduct compound (B).

The boric acid ester (C) is preferably a compound represented by the formula (C).

(In the formula (C), R's are each independently a hydrocarbon group having 1 to 20 carbon atoms and optionally having a substituent, and the hydrocarbon group optionally contains 1 or 2 or more oxygen atoms.)

Examples of the substituent optionally included in R include a hydroxyl group, an amino group, and a carboxyl group. These substituents may be the terminal of the hydrocarbon group or may be present in a part other than the terminal.

R is preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably a linear or branched alkyl group having 1 to 10 carbon atoms) or an unsubstituted aryl group having 6 to 12 carbon atoms (preferably a phenyl group).

The 3R in the formula (C) may be the same or different, and are preferably the same.

The molecular weight of the borate (C) used in this embodiment is preferably 104 to 1500, more preferably 104 to 1000, still more preferably 104 to 500, still more preferably 104 to 350.

Specific examples of the borate (C) used in the present embodiment include trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tripentyl borate, triallyl borate, trihexyl borate, trioctyl borate, triisooctyl borate, trinonyl borate, tridecyl borate, tricodecyl borate, tricetyl borate, trioctadecyl borate, triphenyl borate, tricyclohexyl borate, tribenzyl borate, tricresyl borate, triethanolamine borate, triorthenylborolate, bisphenylhydroborate, bis-2, 3-dimethylethylenephenyl pyroborate, bis-2, 2-dimethyltrimethylene pyroborate, tris (2-ethylhexyl) borane, bis (1, 4,7, 10-tetraoxaundecyl) (1, 4,7,10, 13-pentaoxatetradecyl) (1, 4, 7-trioxaundecyl) borane, 2- (2-dimethyl-3-diethylene-2, 3-dimethyltetramethylene pyroborate, bis (2-ethyl-2-ethylhexyl) borane, bis (1, 4,7,10, 13-pentaoxatetradecyl) (1, 4, 7-trioxaundecyl) borane, 2- (2-dimethyl-3-dioxan-2, 3-dimethyl-2-dimethylethylene pyroborate, 3-dioxan-2-dimethyl-2-ethynyl) -2-ethy-2, 3-dimethylenen-2-dimethyleneborane, 1,4, 10-dioxan-2-dimethyl-2-dioxan 2- (. Beta. -diisopropylaminoethoxy) -4-methyl-1, 3, 2-dioxaborolan, 2- (. Gamma. -dimethylaminopropoxy) -1,3,6, 9-tetraoxa-2-boracycloundecane and 2- (. Beta. -dimethylaminoethoxy) -4,4- (4-hydroxybutyl) -1,3, 2-dioxaborolan, 2-oxybis (5, 5-dimethyl-1, 3, 2-dioxaborolan), etc.

The content of the boric acid ester (C) in the resin composition of the present embodiment is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.08 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, and may be 0.4 part by mass or more, based on 100 parts by mass of the cyanate ester compound (a). When the lower limit value is not less than the above-mentioned lower limit value, stability and curability of the resin composition tend to be further improved. The upper limit of the content of the boric acid ester (C) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less, based on 100 parts by mass of the cyanate ester compound (a). When the upper limit value is not more than the above-mentioned upper limit value, the stability of the resin composition and the heat resistance of the cured product tend to be further improved.

The resin composition of the present embodiment may contain only 1 kind of boric acid ester (C), or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

The mass ratio of the amine adduct compound (B) to the boric acid ester (C) (amine adduct compound (B)/boric acid ester (C)) in the resin composition of the present embodiment is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 1.5 or more. When the lower limit value is not less than the above-mentioned lower limit value, the effect of the present invention tends to be more effectively improved. The mass ratio of the amine adduct compound (B) to the boric acid ester (C) (amine adduct compound (B)/boric acid ester (C)) is preferably 10.0 or less, more preferably 5.0 or less, and still more preferably 3.5 or less. By setting the upper limit value or lower and the lower limit value or higher, the effect of the present invention tends to be more effectively improved.

< Phenol Compound (D) >

The resin composition of the present embodiment preferably contains a phenol compound (D). By containing a phenol compound, curability tends to be further improved.

The phenol compound (D) in the present embodiment is a compound having a structure in which at least a hydroxyl group is directly bonded to a benzene ring, and preferably a compound having a structure in which at least a hydroxyl group is directly bonded to a benzene ring. The phenol compound (D) may be a low molecule or a high molecule. In addition, the benzene ring possessed by the phenol compound (D) may optionally have other substituents than hydroxyl groups. When the benzene ring has a substituent other than a hydroxyl group, it is preferable that 1 to 3 other substituents other than a hydroxyl group are contained in each 1 benzene ring.

Examples of the other substituent include a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, a halogen atom, preferably a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 20 carbon atoms. In addition, 2 other substituents bonded to the benzene ring are optionally bonded to each other to form a ring. Examples of the ring formed by bonding 2 other substituents bonded to the benzene ring include naphthalene ring and indane ring.

The phenol compound (D) used in the present embodiment is preferably a compound having a structure in which 1 or 2 hydroxyl groups are directly bonded to a benzene ring. Examples of the substituent include a hydrocarbon group having 5 to 20 carbon atoms (preferably an alkyl group).

An example of the phenol compound (D) used in the present embodiment is a low molecular compound, for example, a compound having a molecular weight of 94 to 1000, preferably 94 to 500.

Further, another example of the phenol compound (D) used in the present embodiment is a polymer compound, for example, a phenol compound having a molecular weight of more than 1000 and 10 ten thousand or less, preferably a phenol compound having a molecular weight of more than 1000 and 10000 or less.

Specific examples of the phenol compound (D) used in the present embodiment include butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, and p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, catechol, resorcinol, hydroquinone, trihydroxybenzene, styrenated phenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, phenol novolak resin, cresol novolak resin, and xylenol novolak resin, and nonylphenol and dinonylphenol are preferable.

When the resin composition of the present embodiment contains the phenol compound (D), the content thereof is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, still more preferably 5 parts by mass or more, relative to 100 parts by mass of the cyanate compound (a). When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be further improved. The upper limit of the content of the phenol compound (D) is preferably 20 parts by mass or less, more preferably 17 parts by mass or less, still more preferably 14 parts by mass or less, still more preferably 12 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the cyanate compound (a). When the upper limit value is not more than the above-mentioned upper limit value, the heat resistance of the cured product tends to be further improved.

The resin composition of the present embodiment may contain only 1 kind of phenol compound (D) or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

< Toughness-imparting agent (E) >)

The resin composition of the present embodiment may contain a toughness imparting agent (E). By compounding the toughness imparting agent (E), toughness of the obtained cured product can be further improved.

As the toughness imparting agent (E), a resin can be exemplified. One example of the resin as the toughness imparting agent (E) is a thermoplastic resin, and the other example is a powdery resin.

As the thermoplastic resin, a thermoplastic resin having a bond selected from the group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a thioether bond, a sulfone bond, and a carbonyl bond in the main chain, and optionally having a crosslinked structure in part, is generally preferred. The material may have crystallinity or may be amorphous. In particular, at least 1 resin selected from the group consisting of polyamide resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyphenylene sulfide resin, polyarylate resin, polyester resin, polyamideimide resin, polyimide resin, polyetherimide resin, polyimide resin having a phenyltrimethylindane structure, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, polyaromatic amide resin, polyethernitrile resin and polybenzimidazole resin is preferable, and polyimide resin is more preferable.

The polyimide resin may be described in paragraphs 0013 to 0021 of JP 2022-045273A, the contents of which are incorporated herein by reference.

The powdery resin is preferably a powdery thermoplastic resin, and examples thereof include rubber powders such as styrene-type powder, butadiene-type powder and acrylic-type powder, core-shell rubber powder, silicone-type powder, and the like. Among these powdery resins, silicone-type powders are preferable from the viewpoint that the resulting cured product has more excellent rigidity and can further reduce warpage.

Examples of the silicone powder include silicone resin powder, silicone rubber powder, and silicone composite powder. Among these, the silicone composite powder is preferable from the viewpoint of further improving the rigidity of the obtained cured product and further reducing warpage.

Examples of the silicone composite powder include KMP-600 (trade name), KMP-601 (trade name), KMP-602 (trade name), KMP-605 (trade name) and X-52-7030 (trade name) manufactured by Xinyue chemical industries Co., ltd.

When the resin composition of the present embodiment contains the toughness imparting agent (E), the content thereof is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, relative to 100 parts by mass of the cyanate ester compound (a). When the lower limit value is not less than the above-mentioned lower limit value, the toughness of the obtained cured product tends to be further improved. The upper limit of the content of the toughness imparting agent (E) is preferably 40 parts by mass or less, more preferably 38 parts by mass or less, still more preferably 33 parts by mass or less, still more preferably 30 parts by mass or less, and may be 27 parts by mass or less, based on 100 parts by mass of the cyanate ester compound (a). When the upper limit value is not more than the above-mentioned upper limit value, the heat resistance of the cured product tends to be further improved.

The resin composition of the present embodiment may contain only 1 kind of toughness imparting agent (E), or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

< Other thermosetting resin >

The resin composition of the present embodiment may contain other thermosetting resins other than the cyanate ester compound (a), or may not contain them. As other thermosetting resins, epoxy resins, maleimide resins, phenolic resins, polyphenylene ether resins, benzoxazine resins, organic group-modified silicones, alkenyl-substituted nadic imide compounds, and resins having a polymerizable carbon-carbon unsaturated group can be exemplified. For details, reference is made to paragraphs 0020 to 0028, 0054 to 0056, 0067 to 0070, paragraph 0036 to 0070 of JP-A2022-000506, and paragraph 0049 to 0057 of JP-A2022-046517 in International publication No. 2022/034872.

When the resin composition of the present embodiment contains a thermosetting resin other than the cyanate ester compound (a), the content thereof is preferably 5 to 30 parts by mass relative to 100 parts by mass of the resin solid content contained in the resin composition.

The resin composition of the present embodiment may be substantially free of other thermosetting resins other than the cyanate ester compound (a). The substantial absence means that the amount is less than 5 parts by mass, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.1 part by mass or less, based on 100 parts by mass of the resin solid content contained in the resin composition.

< Other ingredients >

The resin composition of the present embodiment may contain a filler (including an inorganic filler, an organic filler, a filler, and the like), a silane coupling agent, a wetting dispersant, a solvent, and the like, in addition to the above-described components. Further, an impact resistance improver, a curing accelerator, a flame retardant, a conductivity imparting agent, a crystal nucleating agent, an ultraviolet absorber, an antioxidant, a shock absorber, an antibacterial agent, an insect repellent, a deodorant, an anti-coloring agent, a heat stabilizer, a mold release agent, an antistatic agent, a plasticizer, a lubricant, a coloring agent, a pigment, a dye, a foaming agent, and the like may be blended. The details thereof can be referred to the descriptions in paragraphs 0057 to 0052 of JP-A2021-195389 and in paragraphs 0040 to 0048 of JP-A2022-046517, and these are incorporated herein by reference.

When the resin composition of the present embodiment contains a filler, the filler is preferably contained in a proportion of 10 to 500 parts by mass relative to 100 parts by mass of the resin solid content. The resin composition of the present embodiment may be substantially free of filler. The filler is not substantially contained in the resin composition, and the content of the filler is less than 10 parts by mass, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less, based on 100 parts by mass of the resin solid content.

< Physical Properties of resin composition >

The viscosity of the resin composition of the present embodiment is preferably 0.05 to 50pa·s at 80 ℃. By setting such viscosity, it can be preferably used as various materials. The viscosity of the resin composition of the present embodiment at 80 ℃ is more preferably 0.10pa·s or more, still more preferably 40pa·s or less, still more preferably 30pa·s or less, still more preferably 20pa·s or less, still more preferably 10pa·s or less, still more preferably 8pa·s or less.

In particular, when the resin composition of the present embodiment is used in a prepreg, the viscosity at 80 ℃ is preferably 0.1pa·s or more, more preferably 2pa·s or more, and further preferably 10pa·s or less, more preferably 8pa·s or less.

The viscosity was measured as described in examples below.

The resin composition of the present embodiment is preferably excellent in stability upon storage. For example, the viscosity of each composition when kept at 80 ℃ for 60 minutes is expressed as a relative viscosity when the viscosity before the start of the test is 100, and is preferably 180 or less, more preferably 150 or less, further preferably 140 or less, further preferably 130 or less, and still further preferably 120 or less. The lower limit of the relative viscosity is preferably 100, and even at least 101 may sufficiently satisfy the performance requirements.

The relative viscosity was measured as described in examples described below.

The resin composition of the present embodiment is preferably excellent in curability. For example, the exothermic behavior of each composition is observed under the measurement conditions of a start temperature of 40 ℃, an end temperature of 380 ℃ and a temperature rise rate of 3 ℃ per minute using a differential scanning calorimeter, and the peak top temperature is preferably 185 ℃ or less, more preferably 180 ℃ or less, still more preferably 175 ℃ or less, still more preferably 170 ℃ or less, still more preferably 165 ℃ or less. The lower limit value of the peak top temperature is preferably 100 ℃ or more, more preferably 110 ℃ or more, still more preferably 120 ℃ or more, still more preferably 130 ℃ or more, still more preferably 135 ℃ or more.

The peak top temperature was measured as described in examples described below.

The resin composition of the present embodiment preferably has high heat resistance. For example, the glass transition temperature of the cured product obtained by heating the resin composition of the present embodiment at 135 ℃ for 8 hours and further at 177 ℃ for 4 hours is preferably 180 ℃ or higher, more preferably 184 ℃ or higher, further preferably 190 ℃ or higher, still more preferably 195 ℃ or higher, still more preferably 200 ℃ or higher. On the other hand, the upper limit of the glass transition temperature is not particularly limited, and 300 ℃ or lower is practical, and the required performance is sufficiently satisfied even at 250 ℃ or lower.

The glass transition temperature (Tg) was measured by a dynamic viscoelasticity analyzer and a DMA method according to JIS C6481, and the initial (onset) value was set as the glass transition temperature (Tg) for the cured product of the resin composition.

The details were measured as described in examples below.

< Use >

The resin composition of the present embodiment can be suitably used as a cured product, a prepreg, a multilayer body, a sealing material, an adhesive, an insulating material, a coating material, or a fiber-reinforced composite material. Hereinafter, these will be described.

< Cured product >

The cured product of the present embodiment is a cured product of the resin composition of the present embodiment. The method for producing the cured product is not particularly limited, and the cured product can be obtained by, for example, melting the resin composition or dissolving the resin composition in a solvent, then flowing the resin composition into a mold, and curing the resin composition under normal conditions using heat, light, or the like. In the case of thermal curing, the curing temperature is not particularly limited, and is preferably in the range of 120 to 300 ℃ from the viewpoint of effectively performing curing and preventing deterioration of the obtained cured product. In the case of photo-curing, the wavelength region of light is not particularly limited, and curing is preferably performed in a range of 100 to 500nm where curing is effectively performed by a photopolymerization initiator or the like.

Prepreg-

The prepreg according to the present embodiment is a prepreg formed from a base material and the resin composition according to the present embodiment. More specifically, the prepreg of the present embodiment includes a base material, and a resin composition and/or a cured product thereof applied (e.g., impregnated or coated) to the base material. That is, in the prepreg, the resin composition may be uncured or may be a cured product containing a semi-cured product. In addition, the solvent may be removed from the resin composition.

The method for producing the prepreg is not particularly limited, and may be carried out according to a conventional method.

For example, the resin composition of the present embodiment may be applied (preferably coated) to a substrate to produce a prepreg. In this case, the resin composition may be heated and applied to the substrate and then returned to normal temperature, or the solvent may be added to the resin composition and applied to the substrate and then removed.

The prepreg of the present embodiment can also be produced by, for example, applying the resin composition of the present embodiment to a substrate, and then semi-curing (B-staging) the substrate by heating the substrate in a dryer at 100 to 200 ℃ for 1 to 30 minutes.

The total amount of the resin solid component and the filler in the resin composition is preferably 30 mass% or more, more preferably 35 mass% or more, further preferably 40 mass% or more, and further preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less, relative to the total amount of the prepreg. When the content of the resin composition is within the above range, the moldability of the prepreg tends to be further improved.

The base material of the prepreg is not particularly limited, and may be appropriately selected and used according to the intended use and performance. Specific examples of the fibers constituting the base material include, but are not particularly limited to, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass, inorganic fibers other than glass such as quartz fibers, carbon fibers, boron fibers, and basalt fibers, wholly aromatic polyamides such as poly (paraphenylene terephthalamide) (Kevlar (registered trademark), manufactured by dupont), copolymerized para (phenylene 3,4' -oxydiphenylene terephthalamide) (manufactured by Technora (registered trademark), manufactured by Teijin Techno Products Limited corporation), polyesters such as 2, 6-hydroxynaphthoic acid parahydroxybenzoic acid (Vectran (registered trademark), manufactured by k corporation), zxion (registered trademark, KB SEIREN, manufactured by ltd), and organic fibers such as poly (paraphenylene benzoxazole) (Xyron (registered trademark), manufactured by eastern corporation), and polyimide. Of these, at least 1 selected from the group consisting of carbon fibers and/or glass fibers is preferable, and carbon fibers are more preferable. These substrates may be used alone or in combination of 1 or more than 2.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, surface mats, and the like. The weaving method of the woven fabric is not particularly limited, and for example, a plain weave, a basket weave, a twill weave, or the like is known, and may be appropriately selected from those known in the art according to the intended use and performance. In addition, a glass fabric obtained by subjecting them to a fiber opening treatment or a surface treatment with a silane coupling agent or the like is suitably used. The thickness and mass of the substrate are not particularly limited, and those of about 0.01 to 0.3mm are usually suitably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a woven fabric of glass fibers and/or carbon fibers.

The multilayer body of the present embodiment is formed of the prepreg of the present embodiment. The multilayer body of the present embodiment is preferably obtained by stacking 2 or more layers of the aforementioned prepregs. In the multilayer body of the present embodiment, the resin composition in the prepreg may be uncured or may be a cured product including a semi-cured product.

The multilayer body of the present embodiment may have other constituent layers within a range not exceeding the resin of the present embodiment.

The prepregs and the multilayer body of the present embodiment can be preferably used as a material application for aerospace.

Sealing Material

The sealing material of the present embodiment contains the resin composition of the present embodiment. As a method for producing the sealing material, generally, a known method can be suitably applied, and is not particularly limited. For example, the sealing material can be produced by mixing the above resin composition with various known additives or solvents commonly used for sealing material applications, using a known stirrer. The method of adding the components at the time of mixing is not particularly limited, and generally known methods can be suitably applied.

Adhesive >

The adhesive of the present embodiment contains the resin composition of the present embodiment. The method for producing the adhesive is not particularly limited, and generally known methods can be suitably applied. For example, the adhesive can be produced by mixing the resin composition with various known additives or solvents commonly used for adhesive applications, using a known stirrer. The method of adding the components at the time of mixing is not particularly limited, and generally known methods can be suitably applied.

Insulating material

The insulating material of the present embodiment includes the resin composition of the present embodiment. As a method for producing the insulating material, a known method can be generally applied appropriately, and is not particularly limited. For example, the insulating material can be produced by mixing the above resin composition with various known additives, solvents, and the like which are generally used for the use of the insulating material, using a known stirrer. The method of adding the components at the time of mixing is not particularly limited, and generally known methods can be suitably applied.

Coating material

The coating material of the present embodiment contains the resin composition of the present embodiment. As a method for producing the paint, generally, a known method can be suitably applied, and is not particularly limited. For example, the resin composition can be mixed with various known additives, solvents, and the like, which are generally used for coating applications, using a known stirrer to produce a coating. The method of adding the components at the time of mixing is not particularly limited, and generally known methods can be suitably applied.

Fiber reinforced composite material

The fiber-reinforced composite material of the present embodiment includes reinforcing fibers and a cured product of the resin composition of the present embodiment. Preferably, the resin composition comprises reinforcing fibers and a cured product obtained by applying (preferably impregnating or coating) the reinforcing fibers and curing the reinforcing fibers.

As the reinforcing fiber, a known one can be used, and is not particularly limited. Specific examples thereof include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, carbon fibers, aramid fibers, boron fibers, PBO fibers, high-strength polyethylene fibers, alumina fibers, and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and may be appropriately selected from woven fabrics, nonwoven fabrics, felts, knitted fabrics, ropes, unidirectional strands, rovings, chopped strands, and the like. As the form of the reinforcing fibers, a preform (a laminate of a woven fabric base fabric made of reinforcing fibers, an article obtained by integrating the reinforcing fibers by sewing with a suture, or a fiber structure such as a three-dimensional woven fabric or a woven fabric) may be used.

As a method for producing these fiber reinforced composite materials, generally, a known method can be suitably applied, and is not particularly limited. Specific examples thereof include a liquid composite molding method, a resin film infiltration method, a filament winding method, a manually-made reinforced plastic film method, a pultrusion method, and the like. Among them, the resin transfer molding method, which is one of the liquid composite molding methods, is preferably used in the case of mass-producing composite materials having relatively complicated shapes in a short time because it is possible to set the raw materials other than the preform, such as a metal plate, a foam core, and a honeycomb core, in a molding die in advance, and thus can cope with various uses.

Examples

The present invention will be described more specifically below with reference to examples. The materials, amounts, ratios, treatment contents, treatment steps and the like shown in the following examples may be appropriately changed within the scope not exceeding the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

When the measurement equipment used in the examples is difficult to obtain due to model discarding or the like, other equipment having the same performance may be used for measurement.

Synthesis example 1 Synthesis of cyanate (SNCN)

In a reactor, 0.47mol (equivalent to OH) of an α -naphthol aralkyl phenol resin (product name: SN495V, OH base equivalent: 236g/eq., manufactured by NIPPON STEEL CHEMICAL & Material Co., ltd., including 1 to 5 of repeating unit number n of naphthol aralkyl) was dissolved in 500mL of chloroform, and 0.7mol of triethylamine was added to the solution. While maintaining the temperature at-10 ℃, 300g of a chloroform solution of 0.93mol of cyanogen chloride was added dropwise to the reactor over 1.5 hours, and after the completion of the addition, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1mol of triethylamine and 30g of chloroform was further added dropwise to the reactor, followed by stirring for 30 minutes, whereby the reaction was completed. After filtering out the hydrochloride of triethylamine as a by-product from the reaction solution, the obtained filtrate was washed with 500mL of 0.1N hydrochloric acid, and then washing with 500mL of water was repeated 4 times. After drying with sodium sulfate, evaporation was performed at 75 ℃, and further, vacuum degassing was performed at 90 ℃, whereby a brown solid α -naphthol aralkyl type cyanate ester resin (hereinafter referred to as SNCN) was obtained. As a result of analysis of the obtained α -naphthol aralkyl type cyanate ester resin by infrared absorption spectrum, absorption of cyanate ester groups around 2264cm ^-1 was confirmed.

< Synthesis example 2 Synthesis of cyanate ester (P-2M) >

In a reactor, 0.5mol (in terms of OH group) of bisphenol M (OH group equivalent: 173g/eq., MITSUI FINE CHEMICALS, INC Co., ltd.) was dissolved in 500mL of chloroform, and 0.75mol of triethylamine was added to the solution. While maintaining the temperature at-10 ℃,300 g of a 1.0mol chloroform solution of cyanogen chloride was added dropwise to the reactor over 1.5 hours, and after the completion of the addition, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1mol of triethylamine and 30g of chloroform was further added dropwise to the reactor, followed by stirring for 30 minutes, whereby the reaction was completed. After filtering out the hydrochloride of triethylamine as a by-product from the reaction solution, the obtained filtrate was washed with 500mL of 0.1N hydrochloric acid, and then washing with 500mL of water was repeated 4 times. After drying it with sodium sulfate, evaporation was performed at 75 ℃, and further, deaeration was performed under reduced pressure at 90 ℃, whereby a pale yellow solid bis-M-type cyanate resin (hereinafter referred to as P-2M) was obtained. As a result of analysis of the obtained double M-type cyanate resin by infrared absorption spectrum, absorption of cyanate groups around 2234cm ^-1 and 2270cm ^-1 was confirmed.

< Preparation of composition >

Example 1

SNCN 50 parts by mass of the cyanate ester compound (A) obtained in Synthesis example 1, 50 parts by mass of bisphenol A cyanate ester (trade name: manufactured by Mitsubishi gas chemical Co., ltd.), AJICURE PN-50 parts by mass of the amine adduct compound (B) (softening temperature 110 ℃ C., manufactured by Ajinomoto Fine-Techno Co., inc.) 1 part by mass, 0.5 part by mass of triethyl borate (manufactured by Tokyo chemical industry Co., ltd.) as the borate ester (C), and 6 parts by mass of 4-nonylphenol (manufactured by Tokyo chemical industry Co., ltd.) as the phenol compound (D) were put into a screw vial, heated, stirred and mixed to obtain a composition.

Example 2

In example 1, a composition was obtained in the same manner as in example 1 except that 0.5 parts by mass of triphenyl borate (manufactured by tokyo chemical industry co., ltd.) was used instead of using 0.5 parts by mass of triethyl borate.

Example 3

In example 1, a composition was obtained in the same manner as in example 1 except that 1 part by mass of AJICURE MY-25 (softening temperature: 130 ℃ C., manufactured by Ajinomoto Fine-Techno Co., inc.) was used instead of AJICURE PN-50 parts by mass.

Example 4

In example 3, a composition was obtained in the same manner as in example 3 except that 0.5 parts by mass of triphenyl borate was used instead of using 0.5 parts by mass of triethyl borate.

Example 5

In example 1, a composition was obtained in the same manner as in example 1 except that 6 parts by mass of 2, 4-dinonylphenol (Yokkaichi Chemical co., ltd.) was used instead of 6 parts by mass of 4-nonylphenol.

Example 6

A composition was obtained in the same manner as in example 1, except that 8 parts by mass of 4-nonylphenol was used in place of 6 parts by mass of 4-nonylphenol in example 1.

Example 7

A composition was obtained in the same manner as in example 1, except that 10 parts by mass of 4-nonylphenol was used in place of 6 parts by mass of 4-nonylphenol in example 1.

Example 8

In example 1, a composition was obtained in the same manner as in example 1 except that 70 parts by mass of a bisphenol A type cyanate ester prepolymer (trade name: manufactured by Mitsubishi gas chemical Co., ltd.) and 30 parts by mass of TA were used instead of SNCN parts by mass and 50 parts by mass of TA, 0.15 part by mass of triethyl borate was used instead of 0.5 part by mass of triethyl borate, and 10 parts by mass of 4-nonylphenol was used instead of 6 parts by mass of 4-nonylphenol.

Example 9

In example 8, a composition was obtained in the same manner as in example 8 except that 0.3 parts by mass of triethyl borate was used instead of 0.15 parts by mass of triethyl borate.

Example 10

In example 8, a composition was obtained in the same manner as in example 8 except that 0.5 parts by mass of triethyl borate was used instead of 0.15 parts by mass of triethyl borate.

Example 11

In example 8, a composition was obtained in the same manner as in example 8 except that 0.7 parts by mass of triethyl borate was used instead of 0.15 parts by mass of triethyl borate.

Example 12

In example 8, a composition was obtained in the same manner as in example 8 except that 0.9 parts by mass of triethyl borate was used instead of 0.15 parts by mass of triethyl borate.

Example 13

In example 8, a composition was obtained in the same manner as in example 8 except that AJICURE PN to 50.5 parts by mass was used instead of AJICURE PN to 50 parts by mass, and 6 parts by mass of 4-nonylphenol was used instead of 10 parts by mass of 4-nonylphenol.

Example 14

In example 13, a composition was obtained in the same manner as in example 13 except that AJICURE PN to 50.5 parts by mass was used instead of AJICURE PN to 50.5 parts by mass and 0.45 part by mass of triethyl borate was used instead of 0.15 part by mass of triethyl borate.

Example 15

A composition was obtained in the same manner as in example 1 except that 25 parts by mass of a thermoplastic polyimide resin (trade name: therplim Mitsubishi gas chemical Co., ltd.) was added as the toughness imparting agent (E) in example 1.

Example 16

In example 1, a composition was obtained in the same manner as in example 1 except that SNCN parts by mass and P-2m 35 parts by mass obtained in synthesis example 2 were used instead of SNCN parts by mass and TA 50 parts by mass.

Example 17

In example 8, a composition was obtained in the same manner as in example 8 except that 90 parts by mass of a prepolymer of bisphenol a type cyanate ester and 10 parts by mass of TA were used instead of 70 parts by mass of a prepolymer of bisphenol a type cyanate ester and 30 parts by mass of TA, 0.4 parts by mass of triethyl borate was used instead of 0.15 parts by mass of triethyl borate, and 9 parts by mass of 4-nonylphenol was used instead of 10 parts by mass of 4-nonylphenol.

Example 18

In example 17, a composition was obtained in the same manner as in example 17 except that 85 parts by mass of a bisphenol a type cyanate ester prepolymer and 15 parts by mass of TA were used instead of 90 parts by mass of the bisphenol a type cyanate ester prepolymer and 10 parts by mass of TA, and Therplim parts by mass of a toughness imparting agent (E) was added.

Example 19

A composition was obtained in the same manner as in example 18 except that 0.5 parts by mass of triethyl borate was used instead of 0.4 parts by mass of triethyl borate in example 18.

Example 20

A composition was obtained in the same manner as in example 18 except that 0.6 parts by mass of triethyl borate was used instead of 0.4 parts by mass of triethyl borate in example 18.

Example 21

A composition was obtained in the same manner as in example 18 except that 0.7 parts by mass of triethyl borate was used instead of 0.4 parts by mass of triethyl borate in example 18.

Example 22

A composition was obtained in the same manner as in example 18 except that 1 part by mass of triethyl borate was used instead of 0.4 part by mass of triethyl borate in example 18.

Example 23

A composition was obtained in the same manner as in example 18 except that 20 parts by mass of a silicone composite powder (trade name: KMP-600, manufactured by Xinyue chemical industries Co., ltd.) was used instead of Therplim parts by mass in example 18.

Example 24

A composition was obtained in the same manner as in example 18 except that 20 parts by mass of a silicone composite powder (trade name: KMP-601, manufactured by Xinyue chemical industries Co., ltd.) was used instead of Therplim parts by mass in example 18.

Example 25

A composition was obtained in the same manner as in example 18 except that 20 parts by mass of a silicone composite powder (trade name: KMP-602, manufactured by Xinyue chemical industries Co., ltd.) was used instead of Therplim parts by mass in example 18.

Example 26

A composition was obtained in the same manner as in example 18 except that 20 parts by mass of a silicone composite powder (trade name: KMP-605, manufactured by Xinyue chemical Co., ltd.) was used in place of Therplim parts by mass in example 18.

Comparative example 1

In example 1, a composition was obtained in the same manner as in example 1 except that 0.5 part by mass of triethyl borate was not used.

Comparative example 2

A composition was obtained in the same manner as in example 3 except that 0.5 parts by mass of triethylborate was not used in example 3.

Comparative example 3

A composition was obtained in the same manner as in example 1 except that AJICURE PN to 50 parts by mass of the composition in example 1 was not used.

Comparative example 4

A composition was obtained in the same manner as in example 2, except that AJICURE PN to 50 parts by mass of the composition in example 2 was not used.

Comparative example 5

A composition was obtained in the same manner as in example 1 except that AJICURE PN-50 parts by mass, 0.5 part by mass of triethyl borate and 6 parts by mass of nonylphenol were not used in example 1.

Comparative example 6

A composition was obtained in the same manner as in example 1 except that AJICURE PN to 50 parts by mass and 0.5 part by mass of triethyl borate were not used in example 1.

Comparative example 7

A composition was obtained in the same manner as in example 8 except that 0.15 parts by mass of triethylborate was not used in example 8.

Comparative example 8

A composition was obtained in the same manner as in example 16 except that 0.5 part by mass of triethylborate was not used in example 16.

Comparative example 9

In comparative example 8, a composition was obtained in the same manner as in comparative example 8 except that 0.1 part by mass of cobalt (III) acetylacetonate (manufactured by tokyo chemical industry co., ltd.) was used instead of AJICURE PN to 50 parts by mass.

< Evaluation of composition >

Each composition obtained in the above-described manner was evaluated for each characteristic according to the following criteria.

(1) Viscosity of the mixture

The viscosity (unit: pa.s) of each composition at 80℃was measured using a dynamic viscoelasticity analysis apparatus.

A dynamic viscoelasticity analysis device was used, and was manufactured by Discovery HR-2, TA Instruments.

(2) Stability of

The viscosity of each composition was measured using a dynamic viscoelasticity analysis device at 80 ℃ for 60 minutes. The relative viscosity after 60 minutes from the start of the test was calculated and the stability was evaluated, assuming that the viscosity before the start of the test was 100.

(3) Curability of

The curability was evaluated by observing the exothermic behavior of each composition under the measurement conditions of a start temperature of 40 ℃, an end temperature of 380 ℃ and a temperature rise rate of 3 ℃ per minute using a differential scanning calorimeter, and obtaining a peak top temperature (unit: °c).

The differential scanning calorimeter was obtained by DSC7020, SII Nanotechnologies.

(4) Heat resistance of cured product

About 6g of each of the compositions obtained in the above-described manner was weighed into an aluminum cup, and heated in a curing oven at 135℃for 8 hours and 177℃for 4 hours, to obtain cured products.

Using the obtained cured product, the storage modulus G' was measured by a dynamic viscoelasticity analyzer according to JIS C6481 and by a DMA method, and the heat resistance of the cured product was evaluated using the initial value as the glass transition temperature (Tg, unit:. Degree.C.).

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

From tables 1 to 6, it was also confirmed that the resin compositions of the present invention using the cyanate ester compound (A), the amine adduct (B) and the boric acid ester (C) had stability and curability, and that the cured products thereof had excellent heat resistance (high glass transition temperature).

Claims

1. A resin composition comprising a cyanate compound (A), an amine adduct compound (B) and a borate ester (C).

2. The resin composition according to claim 1, wherein the cyanate compound (A) comprises at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II),

In formula (I), Ar ₁ each independently represents an aromatic ring; Ra each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or aryl group in Ra may have a substituent; a represents the number of bonds of cyanooxy groups bonded to Ar ₁ , and each independently represents an integer of 1 to 3; b represents the number of bonds of Ra bonded to Ar ₁ , and each independently represents a number obtained by subtracting (a+2) from the number of substitutable groups of Ar ₁ ; c is an integer of 1 to 50; X each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms, a sulfonyl group (-SO ₂ -), a divalent sulfur atom (-S-), or a divalent oxygen atom (-O-),

In formula (II), _Ar2 represents an aromatic ring; Rb each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; the alkyl group or aryl group in Rb optionally has a substituent; d represents the number of bonds of the cyano group bonded to _Ar2 , which is an integer of 2 to 3; e represents the number of bonds of Rb bonded to _Ar2 , which is the number obtained by subtracting (d+2) from the number of substitutable groups of _Ar2 .

3. The resin composition according to claim 2, wherein X in the formula (I) each independently represents a divalent linking group selected from the group consisting of the following formulae (III) to (XIV),

In formula (III), Ar ₃ each independently represents an aromatic ring; Rc, Rd, Rg and Rh each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the alkyl group or aryl group in Rc, Rd, Rg and Rh may optionally have a substituent; Re and Rf each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or aryl group in Re and Rf may optionally have a substituent; f represents an integer from 0 to 5,

In formula (IV), Ar ₄ each independently represents an aromatic ring; Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or aryl group in Ri and Rj may have a substituent; g represents an integer of 0 to 5,

In the formula (VIII), h represents an integer of 4 to 7; and in the formula (XIII), Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

4. The resin composition according to any one of claims 1 to 3, wherein the cyanate compound (A) comprises at least one selected from the group consisting of a compound represented by the following formula (XV) and a compound represented by the following formula (XVI),

In formula (XV), Ar ₅ each independently represents an aromatic ring; Rl each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxymethylene group, and a group obtained by linking two or more of these groups; Rm and Rn each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or aryl group in Rm and Rn optionally has a substituent; i represents the number of bonds of the cyano group bonded to Ar ₅ , which is an integer of 1 to 3; j represents the number of bonds of Rm bonded to Ar ₅ , which is a number obtained by subtracting (i+2) from the number of substitutable groups of Ar ₅ ; k represents the number of bonds of Rn bonded to Ar ₅ , which is a number obtained by subtracting 2 from the number of substitutable groups of Ar ₅ ; l represents an integer greater than 1; m represents an integer greater than 1; the arrangement of each repeating unit is arbitrary,

In formula (XVI), Ar ₆ each independently represents an aromatic ring; Ro each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group or an oxymethylene group, or a group obtained by linking them; Rp and Rq each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the alkyl group or aryl group in Rp and Rq optionally has a substituent; n represents the number of bonds of the cyano group bonded to Ar ₆ , which is an integer of 2 to 3; o represents the number of bonds of Rp bonded to Ar ₆ , which is the number obtained by subtracting (n+2) from the number of substitutable groups of Ar ₆ ; p represents the number of bonds of Rq bonded to Ar ₆ , which is the number obtained by subtracting 2 from the number of substitutable groups of Ar ₆ ; q represents an integer greater than 1.

5 . The resin composition according to claim 1 , wherein the content of the amine adduct compound (B) is 0.01 to 30 parts by mass based on 100 parts by mass of the cyanate compound (A).

6 . The resin composition according to claim 1 , wherein the content of the boric acid ester (C) is 0.01 to 15 parts by mass based on 100 parts by mass of the cyanate ester compound (A).

7 . The resin composition according to claim 1 , further comprising a phenol compound (D).

8 . The resin composition according to claim 7 , wherein the content of the phenol compound (D) is 1 to 20 parts by mass based on 100 parts by mass of the cyanate compound (A).

9 . The resin composition according to claim 1 , further comprising a toughening agent (E).

10 . The resin composition according to claim 9 , wherein the toughening agent (E) comprises a thermoplastic resin.

11 . The resin composition according to claim 9 , wherein the toughening agent (E) comprises a powdery resin.

12 . The resin composition according to claim 9 , wherein the content of the toughening agent (E) is 1 to 40 parts by mass based on 100 parts by mass of the cyanate compound (A).

13. The resin composition according to any one of claims 1 to 11, wherein the content of the amine adduct compound (B) is 0.01 to 30 parts by mass based on 100 parts by mass of the cyanate compound (A).

The content of the boric acid ester (C) is 0.01 to 15 parts by mass relative to 100 parts by mass of the cyanate ester compound (A).

The resin composition further comprises a phenol compound (D),

14 . The resin composition according to claim 13 , further comprising a toughening agent (E), wherein the content of the toughening agent (E) is 1 to 40 parts by mass based on 100 parts by mass of the cyanate compound (A).

15 . A cured product, which is a cured product of the resin composition according to claim 1 .

16 . A sealing material comprising the resin composition according to claim 1 .

17 . An adhesive comprising the resin composition according to claim 1 .

18 . An insulating material comprising the resin composition according to claim 1 .

19. A coating material comprising the resin composition according to any one of claims 1 to 14.

20 . A prepreg comprising a base material and the resin composition according to claim 1 .

21. A multilayer body formed from the prepreg according to claim 20.

22. A fiber-reinforced composite material comprising reinforcing fibers and a cured product of the resin composition according to any one of claims 1 to 14.